WO2012107887A2 - Procédé d'application d'une composition de soins capillaires sur les cheveux - Google Patents
Procédé d'application d'une composition de soins capillaires sur les cheveux Download PDFInfo
- Publication number
- WO2012107887A2 WO2012107887A2 PCT/IB2012/050566 IB2012050566W WO2012107887A2 WO 2012107887 A2 WO2012107887 A2 WO 2012107887A2 IB 2012050566 W IB2012050566 W IB 2012050566W WO 2012107887 A2 WO2012107887 A2 WO 2012107887A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- support
- composition
- hair
- cavities
- droplets
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D19/00—Devices for washing the hair or the scalp; Similar devices for colouring the hair
- A45D19/02—Hand-actuated implements, e.g. hand-actuated spray heads
- A45D19/028—Hand-actuated implements, e.g. hand-actuated spray heads having applicators other than brushes or combs, e.g. rollers, balls or sponges
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D34/00—Containers or accessories specially adapted for handling liquid toiletry or cosmetic substances, e.g. perfumes
- A45D34/04—Appliances specially adapted for applying liquid, e.g. using roller or ball
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers for dispensing liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant
- B65D83/75—Aerosol containers not provided for in groups B65D83/16 - B65D83/74
- B65D83/753—Aerosol containers not provided for in groups B65D83/16 - B65D83/74 characterised by details or accessories associated with outlets
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D2200/00—Details not otherwise provided for in A45D
- A45D2200/05—Details of containers
- A45D2200/054—Means for supplying liquid to the outlet of the container
- A45D2200/057—Spray nozzles; Generating atomised liquid
Definitions
- the present invention relates to treatments for keratinous substances or mucous membranes, in particular treatments for caring for or making up the skin, lips or hair.
- the present invention relates in particular, but not exclusively, to styling and shaping hair.
- Application US 2006/247585 discloses disposal applicators in the shape of hand or finger mitts, gloves, flat or tubular pads, wraps, facemasks, booties, to manually apply controllable amounts of lotions, creams, gels or dry powders onto target skin and hard surfaces.
- the most widespread devices for shaping and/or setting hair are aerosol systems that deliver droplets of a hair care product propelled by a gas, generally liquefied, based upon an alcoholic or aqueous solution and polymer resins, forming fine joins between hairs when dry.
- Patent US 5 761 824 discloses a moisturizing attachment for use with a conventional hand held hair dryer.
- the attachment includes a hollowed interior holding compartment for storing a quantity of a moisturizing means, as pebbles, able to trap volume of the fluid in the spaces between them.
- Application GB 2 419 089 describes a method of hair treatment using a foraminous bag containing a fibrous or leaf like material suitable for treatment of hair; and a second hair treating material deposited on the outside surface of the bag.
- the invention aims to meet at least one of these needs.
- the invention relates to a process of holding the hair style by depositing a composition comprising a setting agent on the surface of hair.
- the subject of the present invention is a process for non-therapeutic treatment of human keratinous substances or mucous membranes, comprising the step consisting in:
- the cavities each trap a drop of composition by capillary action.
- the droplets are then deposited on keratinous substances or mucous membranes according to an arrangement depending on the distribution of cavities in the support.
- the process is for example a process for styling and treating hair, the composition being a hair care composition.
- This type of application does not destroy the hair style and, without pressing or rubbing the support on the hair, delivers a setting effect of very high quality, equivalent for example to the result obtained with a conventional aerosol lacquer, without its drawbacks. In particular, it distributes the product for hair care treatment well.
- the support constitutes an application device or belongs to an application device.
- the composition can be applied precisely, without dripping.
- the invention gives hair natural and long-lasting hold.
- the characteristics of the droplets that are deposited onto the hair can easily be controlled, in particular their size, by selecting the sizes of the cavities: finer droplets give the hair a lighter, more natural feel, whereas droplets with higher diameter give a stronger hold.
- the characteristics of the support may be adapted depending on the type of application targeted, in particular weaker or stronger styling, hair design or setting, for example by selecting higher or lower cavity density and/or selecting the material of which the support is made.
- the surface tensions observed in the cavities depend on the material selected.
- the surface is perfectly hydrophobic, it is difficult or even impossible to create droplets of water or aqueous composition that have satisfactory size. If the surface is very hydrophilic, the droplets cannot be transferred easily.
- the material of the support may create different surface tensions depending on the cavities; these mean that some cavities only trap some elements of the composition and that others trap different elements.
- Each cavity in the support may contain one droplet.
- the largest opening size, in particular the diameter of each cavity varies preferably from 30 ⁇ to 3 mm and, so that the droplet released by the cavity has a volume varying from 0.0001 ⁇ to 10 ⁇ and more particularly from 0.001 ⁇ to 3 ⁇ .
- the cavities may not communicate between themselves, which is in particular the case when the cavities are formed by the mesh of a grid or when they are formed at the tip of studs or pins.
- the support may present portions in relief comprising the cavities.
- the cavities form hollow tips of portions in relief. These hollow tips may have a semi- spherical shape.
- the number of cavities may vary from 1 to 100,000, preferably from 50 to
- the cavities extending for example on a surface area of the support varying from 1 to 1,000 cm 2 , preferably from 5 to 500 cm 2 .
- the process according to the invention may be implemented on dry hair or wet hair.
- the hair is preferably dry.
- the support may be brought into contact with the hair.
- the droplets would then be transferred to the hair by capillary action.
- a mechanical action in addition to putting the support in contact with the hair, a mechanical action, exerted for example by the user, contributes to the ejection of droplets.
- the support is not put in contact with the hair but is placed at a distance close enough, for example less than 20 cm, preferably less than 5 cm, and the droplets are ejected by a mechanical action.
- Mechanism action is understood to denote any action by which the droplets are subjected to a physical phenomenon causing them to move from the cavities towards the hair.
- the mechanical action may be an acceleration of the support and/or a variation of pressure in the area around the droplet or a perturbation such as a vibration. This may be a modification to the shape of the cavity.
- the cavities allow droplets to be ejected on demand, the cavities are qualified as active cavities.
- the mechanical action may be caused by a source of vibrations, for example a piezoelectric element or a centrifugal weight, by a pressure source, or a thermal or electric phenomenon.
- the mechanical action may be generated by an ejection system belonging to the device, for example integrated into the support or coupled to it.
- the support is for example subjected to an acceleration due to the user tapping the support, for example when it is located near or in contact with the hair, which has the effect of depositing the drops of product on the hair, or to vibrations generated by a vibrating source.
- the support may be subjected, for example on an opposite face compared to the application face facing the hair, to a pressure increase due to a gas, for example air blown through the support.
- the droplets may be ejected using a gas jet, preferably coming from a container of compressed air.
- the droplet of composition contained in a cavity may also be subjected to a bubble of vapor obtained by heating the composition, this bubble of vapor causing, by slackening, the ejection of the droplet.
- the cavities of the support may cross through it or not. Cavities that cross through are preferred when the ejection of droplets and/or their transfer to hair is caused or assisted by a gas, preferably air, blown behind the support in the direction of the hair.
- the support may be withdrawn and the droplets of composition may be dried on the hair, for example using a hair dryer or helmet dryer, or they may be left to dry naturally.
- the support placed in contact with the hair or held at a distance from the hair, is subjected to an air jet.
- the air jet By using an air jet, the droplets may be transferred and dried on the hair almost simultaneously.
- the air jet allowing or facilitating the droplets of composition to be transferred onto the hair, may be a jet of hot, cold or room-temperature air.
- the air jet may be produced by a source of compressed air or the blowing from a hair dryer or helmet dryer.
- composition may be transferred by exerting several combined actions, for example by tapping the support while subjecting it to a puff of gas.
- the support may be configured to store the droplets of composition and eject them upon demand.
- the device may be controlled to eject the droplets automatically, the ejection taking place for example from all the cavities or only some cavities, in the case where the device allows the ejection by one cavity to be controlled individually.
- Ejection upon demand of droplets may result from a thermal effect or use of a piezoelectric element.
- the device makes it possible to heat the composition, in particular within a cavity to cause it to vaporize and generate an excess pressure that causes a droplet to be ejected and transferred to the hair.
- This technique is related to the thermal process for the ink-jet printing technique, and may be used to cause the composition to be transferred on demand selectively.
- the support may integrate one or more electric resistances that vaporize the composition.
- the droplets may also be ejected from the support by a piezoelectric element.
- a piezoelectric element may allow ejection on demand, this piezoelectric element optionally being combined with one or more specific cavities.
- the interior volume of the cavities varies under the effect of one or more piezoelectric elements, and droplets are ejected and transferred to the hair. This technique is related to the piezoelectric process for the ink-jet printing technique.
- the device according to the invention may be devoid of any electric component, so as to be made at low cost.
- the support may comprise a simple mesh made of a non- absorbent material.
- the process according to the invention may comprise a prior step consisting in loading the support with the hair care composition to be applied.
- the support may be supplied with composition, or loaded with composition before each use.
- the support may be supplied with the composition automatically or not.
- the support may be part of a device that comprises a reservoir containing the composition to be applied.
- the cavities may each communicate, if need be, with the reservoir.
- the composition may be sampled directly by the support from a container containing the composition.
- the support may for example be pressed onto a sponge soaked with composition, so as to be loaded with composition.
- the support is submerged in the composition.
- the support may also be brought into contact with a roll loaded with composition.
- the support may be cleaned after use and the composition remaining on the support after use may be removed easily, for example being cleaned with water or using any suitable solvent, by using an absorbent cloth, by aspiration or by gas jet, this list not being limiting.
- the support may be reloaded with composition means it may be reused.
- the support is for example reloaded with a composition identical to the composition used previously, or the support may be loaded with a different composition.
- the composition being loaded on the support may involve the excess composition on the support being removed, so that the composition is not present anywhere other than in the cavities.
- the support may be brought into contact with a scraper after immersion in a reservoir containing the composition, this scraper being for example formed by the free edge of one wall of the container containing the composition.
- the support comprises tips or studs carrying at their ends the cavities
- the support is loaded by bringing the tips in contact with the composition.
- compositions that may be used in the present invention are in the form of liquids or gel creams, pastes, comprising or not comprising a granular or powder phase.
- the composition When the composition is liquid, it may be in the form of lotion or emulsion
- the composition is in the form of a liquid, a lotion or a fluid emulsion or a gel that is not very thick.
- the viscosity of the composition varies preferably from 1 and 200 cps at 25°C and at a shear rate of Is "1 .
- the viscosity measurements to which reference is made in the present application are measured using a rheometer with cone-plate geometry.
- a composition known to the person skilled in the art for styling and setting hair may be selected and in particular, those added to aerosol devices in the presence of a propellant gas to be used in lacquer form.
- the composition comprises at least one setting agent, as needed in a cosmetically acceptable medium, this medium preferably being water-, alcohol- or aqueous alcohol-based.
- the cosmetic composition according to the invention may also comprise one or more organic solvents, preferably in an amount between 0.05 and 95% weight, very preferably between 1 and 70% by weight, relative to the total weight of the composition.
- This organic solvent may be a C 2 to C 4 lower alcohol, in particular ethanol and isopropanol, polyols and polyol ethers such as propylene glycol, polyethylene glycol or glycerol.
- the organic solvent is preferably ethanol or isopropanol, and even more preferably is ethanol.
- the composition may further comprise one or more fixing polymers as setting agents.
- fixing polymer is understood within the meaning of the present invention to be any polymer that makes it possible to give a shape to the hair or to hold the hair in a given shape.
- All the anionic, cationic, amphoteric and nonionic fixing polymers and mixtures thereof used may be used as fixing polymers in the compositions according to the present application.
- the fixing polymers may be soluble in the cosmetically acceptable medium or insoluble in this same medium and used in this case in the form of dispersions of solid or liquid particles of polymer (latex or pseudolatex).
- the anionic fixing polymers generally used are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acids and have an average molecular weight by number of between about 500 and 5,000,000.
- the carboxylic groups are provided by unsaturated mono- or diacid carboxylic monomers such as those that have the formula:
- n is an integer from 0 to 10
- Ai denotes a methylene group optionally joined to the carbon atom of the unsaturated group or to the adjacent methylene group when n is greater than 1 , via a heteroatom such as oxygen or sulfur
- R 7 denotes a hydrogen atom or a phenyl or benzyl group
- Rs denotes a hydrogen atom or a lower alkyl or carboxyl group
- R9 denotes a hydrogen atom, a lower alkyl group, a CH 2 -COOH, phenyl or benzyl group.
- a lower alkyl group preferably denotes a group containing 1 to 4 carbon atoms and in particular methyl and ethyl groups.
- the anionic fixing polymers containing carboxylic groups that are preferred according to the invention are:
- acrylic acid/ethyl acrylate/N-teri- butylacrylamide terpolymers such as Ultrahold Strong sold by BASF. Mention may also be made of copolymers of acrylic acid and C1-C4 alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and C
- methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers in an aqueous dispersion sold as Amerhold® DR 25 by Amerchol;
- Crotonic acid copolymers such as those comprising vinyl acetate or propionate units in their chain and optionally other monomers such as allyl esters or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon-based chain, such as those containing at least 5 carbon atoms, it being possible for these polymers optionally to be grafted or crosslinked, or alternatively another vinyl, allyl or methallyl ester monomer of an [alpha]- or [beta]-cyclic carboxylic acid.
- Copolymers of C4-C8 monounsaturated carboxylic acids or anhydrides selected from: copolymers comprising (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) at least one monomer selected from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers optionally being monoesterified or monoamidated.
- copolymers comprising (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) at least one monomer selected from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers optionally being monoesterified or monoamidated.
- copolymers comprising (i) one or more maleic, citraconic or itaconic anhydride units and (ii) one or more monomers selected from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, [alpha] -olefin, acrylic or methacrylic ester, acrylic or methacrylic acid or vinylpyrrolidone groups in their chain, the anhydride functions of these copolymers optionally being monoesterified or monoamidated.
- These polymers are described, for example, in French patents 2 350 384 and 2 357 241 of the applicant.
- Homopolymers and copolymers comprising sulfonic groups such as polymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic or acrylamidoalkylsulfonic units, different from the branched sulfonic polyesters of the invention.
- These polymers may in particular be selected from: salts of polyvinylsulfonic acid having a molecular weight between about 1,000 and 100,000, and copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and esters thereof, and acrylamide or derivatives thereof, vinyl ethers and vinylpyrrolidone; salts of polystyrene- sulfonic acid such as sodium salts sold for example as Flexan ® 500 and Flexan ® 130 by National Starch.
- the anionic fixing polymers are preferably selected from copolymers of acrylic acid or of acrylic esters, such as the acrylic acid/ethyl acrylate/N-teri-butylacrylamide terpolymers sold especially as Ultrahold® Strong by BASF, copolymers derived from crotonic acid, such as vinyl acetate/vinyl tert- butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold especially as Resin 28-29-30 by National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives and acrylic acid and esters thereof, such
- the cationic setting film-forming polymers that may be used according to the present invention are preferably selected from polymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the polymer chain or directly attached thereto, and having preferably a molecular weight of between 500 and about 5,000,000 and preferably between 1,000 and 3,000,000.
- these polymers mention may be made more particularly of the following cationic polymers:
- R3 designates a hydrogen atom or a CH3 radical
- A is a linear or branched alkyl group comprising from 1 to 6 carbon atoms or a hydroxyalkyl group comprising from 1 to 4 carbon atoms
- X designates a methosulfate anion or a halide such as chloride or bromide.
- Copolymers from the family (1) further contain one or more units derived from comonomers that may be selected from the family of acrylamides, methacrylamides, diacetones-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups (C1 -C4), groups derived from acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcapro lactam, and vinyl esters.
- comonomers may be selected from the family of acrylamides, methacrylamides, diacetones-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups (C1 -C4), groups derived from acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcapro lactam, and vinyl esters.
- copolymers of dimethylaminoethyl acrylamide and methacrylate quaternized with dimethyl sulfate or with a dimethyl halide such as that sold as Hercofloc® by Hercules
- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold as Bina Quat P 100 by Ciba Geigy the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate such as that sold as Reten by Hercules, vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, quaternized or not, such as the products sold as Gafquat ® by ISP such as for example Gafquat ® 734 or Gafquat ® 755 or the
- non-cellulosic cationic polysaccharides preferably containing quaternary ammonium, such as those described in US patents 3 589 578 and 4 031 307, such as guar gums containing trialkylammonium cationic groups.
- non-cellulosic cationic polysaccharides preferably containing quaternary ammonium, such as those described in US patents 3 589 578 and 4 031 307, such as guar gums containing trialkylammonium cationic groups.
- Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by Meyhall;
- chitosans or salts thereof are, in particular, chitosan acetate, lactate, glutamate, gluconate or pyrrolidonecarboxylate.
- chitosan having a degree of deacetylation of 90.5% by weight, sold as Kytan Brut Standard by Aber Technologies, and chitosan pyrrolidonecarboxylate sold as Kytamer® PC by Amerchol.
- cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and disclosed in particular in US patent 4 131 576, such as hydroxyalkylcelluloses, for example hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted in particular with a methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
- the products sold corresponding to this definition are, more particularly, the products sold as Celquat L 200 and Celquat H 100 by National Starch.
- B and C may also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulfonic group connected via a hydrocarbon group or alternatively B and C form part of a chain of a polymer containing an [alpha], [beta] -dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups.
- amphoteric fixing polymers corresponding to the definition given above that are more particularly preferred are selected from the following polymers:
- copolymers having acidic vinyl units and basic vinyl units such as those resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha- chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamides and acrylamides.
- a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha- chloroacrylic acid
- a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamides and acrylamides.
- At least one basic comonomer such as esters with primary, secondary, tertiary or quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
- the N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are compounds in which the alkyl groups contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-feri-butylacrylamide, ⁇ N-tert- octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides .
- the acidic comonomers are selected more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic or fumaric acid or anhydride.
- the preferred basic comonomers are aminoethyl, butylaminoethyl, ⁇ , ⁇ '- dimethylaminoethyl and N-teri-butylamino ethyl methacrylates.
- copolymers whose CTFA (4th edition, 1991) name is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold as Amphomer® or Lovocryl® 47 by National Starch, are particularly used.
- RIO represents a divalent group derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids, or a group derived from the addition of any one of said acids to a bis(primary) or bis(secondary) amine
- Z denotes a group derived from a bis(primary), mono- or bis(secondary) polyalkylene-polyamine and preferably represents:
- this group being derived from diethylenetriamine, from triethylenetetramine or from dipropy lenetriamine ;
- polyamino amides in proportions of from 0 to 20 mol%, the -NH-(CH 2 )6-NH- group being derived from hexamethylenediamine, these polyamino amides being crosslinked by addition reaction of a bifunctional crosslinking agent selected from epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives, using from 0.025 to 0.35 mol of crosslinking agent per amine group of the polyamino amide and acylated by the action of acrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.
- a bifunctional crosslinking agent selected from epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives
- the saturated carboxylic acids are preferably selected from acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid, acids containing an ethylenic double bond such as, for example, acrylic acid, methacrylic acid and itaconic acid.
- the alkane sultones used in the acylation are preferably propane sultone or butane sultone; the salts of the acylating agents are preferably the sodium or potassium salts.
- Rl 1 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
- y and z represent an integer from 1 to 3
- R12 and R13 represent a hydrogen atom, a methyl, ethyl or propyl group
- R14 and R15 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R14 and R15 does not exceed 10.
- the polymers comprising such units may also comprise units derived from non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
- methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate copolymers such as the product sold as Diaformer Z301 by Sandoz;
- R16 represents a group of formula:
- R20 represents a hydrogen atom, a CH 3 0, CH 3 CH 2 0 or phenyl group
- R21 denotes a hydrogen atom or a lower alkyl group such as methyl or ethyl
- R22 denotes a hydrogen atom or a Ci-C 6 lower alkyl group such as methyl or ethyl
- R23 denotes a Ci-C 6 lower alkyl group such as methyl or ethyl or a group corresponding to the formula: -R24- N(R22)2, R24 representing a group -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - or -CH 2 -CH(CH 3 )-, R22 having the meanings mentioned above.
- E or E' may be identical or different and denote a divalent group that is an alkylene group with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted by hydroxyl groups and which may comprise, in addition to oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups.
- E denotes the symbol E or E' and at least once E';
- E having the meaning given above and E' is a divalent group that is an alkylene group with a straight or branched chain having up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl groups and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain that is optionally interspersed by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloro acetate.
- (9) (Ci-C5)Alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an ⁇ , ⁇ -dialkylaminoalkylamine such as N,N- dimethylaminopropylamine or by semiesterification with an N,N-dialkylaminoalkanol.
- These copolymers may also comprise other vinyl comonomers such as vinylcaprolactam.
- amphoteric fixing polymers described above are those of class (3), such as the copolymers whose CTFA name is Octylacrylamide/acrylates/butylamino ethyl methacrylate copolymer, such as the products sold as Amphomer®, Amphomer® LV 71 or Lovocryl® 47 by National Starch and those of class (4) such as the copolymers of methyl methacrylate/methyl dimethylcarboxy-methylammonioethyl methacrylate, sold, for example, as Diaformer Z301 by Sandoz.
- class (3) such as the copolymers whose CTFA name is Octylacrylamide/acrylates/butylamino ethyl methacrylate copolymer, such as the products sold as Amphomer®, Amphomer® LV 71 or Lovocryl® 47 by National Starch
- class (4) such as the copolymers of methyl methacrylate/methyl dimethylcarboxy-methylammonioethyl methacryl
- the nonionic fixing polymers that may be used according to the present invention are selected, for example, from:
- vinyl acetate copolymers for example copolymers of vinyl acetate and of acrylic ester; copolymers of vinyl acetate and ethylene, or copolymers of vinyl acetate and maleic ester, for example dibutyl maleate;
- acrylic ester homopolymers and copolymers for example copolymers of alkyl acrylates and of alkyl methacrylates, such as the products sold by Rohm & Haas as Primal® AC261 K and Eudragit® NE 30 D, by BASF as 8845, or by Hoechst as Appretan® N9212;
- styrene copolymers for example copolymers of styrene and of alkyl (meth)acrylate, such as the products Mowilith® LDM 691 1, Mowilith® DM 611 and Mowilith® LDM 6070 sold by Hoechst, and the products Rhodopas® SD 215 and Rhodopas® DS 910 sold by Rhone Poulenc; copolymers of styrene, of alkyl methacrylate and of alkyl acrylate; copolymers of styrene and of butadiene; or copolymers of styrene, of butadiene and of vinylpyridine;
- alkyl (meth)acrylate such as the products Mowilith® LDM 691 1, Mowilith® DM 611 and Mowilith® LDM 6070 sold by Hoechst, and the products Rhodopas® SD 215 and Rhodopas® DS 910 sold by
- vinyllactam homopolymers such as vinylpyrrolidone homopolymers and such as the polyvinylcaprolactam sold as Luviskol® Plus by BASF; and
- vinyllactam copolymers such as a poly(vinylpyrrolidone/vinyllactam) copolymer sold under the trade name Luvitec® VPC 55K65W by BASF, poly(vinylpyrrolidone/vinyl acetate) copolymers, such as those sold as PVPVA® S630L by ISP, Luviskol® VA 73, VA 64, VA 55, VA 37 and VA 28 by BASF; and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers, for example the product sold as Luviskol® VAP 343 by BASF.
- a poly(vinylpyrrolidone/vinyllactam) copolymer sold under the trade name Luvitec® VPC 55K65W by BASF poly(vinylpyrrolidone/vinyl acetate) copolymers, such as those sold as PVPVA® S630L by ISP, Luviskol® VA 73,
- the alkyl groups of the nonionic polymers mentioned above preferably have from 1 to 6 carbon atoms.
- fixing polymers of grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, and the other being grafted onto said main chain.
- These polymers are described, for example, in patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0 582 152 and WO 93/23009 and patents US 4 693 935, US 4 728 571 and US 4 972 037.
- These polymers may be amphoteric, anionic or nonionic, and are preferably anionic or nonionic.
- Such polymers are, for example, copolymers that may be obtained by free radical polymerization from the monomer mixture formed from:
- v is a number ranging from 5 to 700, the weight percentages being calculated relative to the total weight of the monomers.
- grafted silicone polymers are, in particular, polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, mixed polymer units of the poly(meth)acrylic acid type and of the polyalkyl (meth)acrylate type and polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, polymer units of the polyisobutyl (meth)acrylate type.
- PDMSs polydimethylsiloxanes
- silicone fixing polymer Another type of silicone fixing polymer that may be mentioned is the product Luviflex ® Silk sold by BASF.
- fixing polymers it is also possible to use functionalized or non- functionalized, cationic, nonionic, anionic or amphoteric, silicone or non-silicone polyurethanes, or mixtures thereof.
- polyurethanes used in the present invention are those in particular disclosed in patent applications EP 0 751 162, EP 0 637 600, EP 0 648 485 and FR 2 743 297, of which the Applicant is the Proprietor, and patent applications EP 0 656 021 and WO 94/03510 from BASF and EP 0 619 111 from National Starch.
- Polyurethanes particularly suitable in the present invention include the products sold as Luviset PUR ® and Luviset ® Si PUR by BASF.
- the concentration of setting polymer(s) used in the compositions according to the present invention is between 0.1% and 20% and preferably between 0.5% and 10% by weight relative to the total weight of the composition.
- composition according to the invention may comprise other additives such as surfactants, cyclic, linear or branched, silicones that are volatile or involatile, and unmodified or modified with organic groups, having a viscosity from 5 X 10 "6 at 2.5 m 2 /s at 25°C, and preferably l x lO "5 at 1 m 2 /s.
- additives such as surfactants, cyclic, linear or branched, silicones that are volatile or involatile, and unmodified or modified with organic groups, having a viscosity from 5 X 10 "6 at 2.5 m 2 /s at 25°C, and preferably l x lO "5 at 1 m 2 /s.
- the silicones that may be used in accordance with the invention may be soluble or insoluble in the composition and in particular may be polyorganosiloxanes that are insoluble in the composition of the invention. They may be in the form of oils, waxes, resins or gums. They may be volatile or involatile.
- the silicones are more particularly selected from those with a boiling point of between 60°C and 260°C.
- the silicones as described above may be used, alone or as a mixture, in an amount of between 0.01% and 20%> by weight and preferably between 0.1 % and 5% by weight.
- compositions of the invention may also comprise non-silicone fatty substances such as mineral, plant, animal and synthetic oils, waxes, fatty esters, ethoxylated or non-ethoxylated fatty alcohols, and fatty acids.
- non-silicone fatty substances such as mineral, plant, animal and synthetic oils, waxes, fatty esters, ethoxylated or non-ethoxylated fatty alcohols, and fatty acids.
- oils that may be used in the composition of the invention, examples that may be mentioned include:
- hydrocarbon-based oils of animal origin such as perhydrosqualene
- hydrocarbon-based oils of plant origin such as liquid fatty acid triglycerides comprising from 4 to 10 carbon atoms, for example heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for example those sold by Stearineries Dubois or those sold as Miglyol ® 810, 812 and 818 by Dynamit Nobel, jojoba oil and shea butter oil; linear or branched hydrocarbons, of inorganic or synthetic origin, such as paraffin oils, volatile or involatile, and derivatives thereof, Vaseline, polydecenes, hydrogenated polyisobutene such as Parleam ® ; isoparaffins such as isohe
- the wax or waxes are selected in particular from carnauba wax, candelilla wax, esparto grass wax, paraffin wax, ozokerite, plant waxes such as olive wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant blossom sold by Bertin (France), animal waxes, for example beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy raw materials that may be used according to the invention are especially marine waxes such as the product sold by Sophim under the reference M82, and polyethylene waxes or polyolefm waxes in general.
- the saturated or unsaturated fatty acids are more particularly selected from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.
- the fatty esters are especially carboxylic acid esters, in particular mono-, di-, tri-, or tetracarboxylic esters.
- the carboxylic acid esters are especially esters of saturated or unsaturated, linear or branched C1-C26 aliphatic acids and of saturated or unsaturated, linear or branched C1-C26 aliphatic alcohols, the total carbon number of the esters being greater than or equal to 10.
- fatty alcohols mention may be made of linear or branched, saturated or unsaturated fatty alcohols containing from 8 to 26 carbon atoms, for example cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.
- the non-silicone fatty substances in general represent from 0.1 to 50%; preferably from 1 to 30%, and more preferably still from 2 to 20% by weight of the total composition.
- setting products can be used that are not used or not often used in the form of aerosol lacquers for reasons of incompatibility with spraying.
- composition according to the invention may also comprise one or more thickening agents.
- the term “thickening agent” means an agent capable, by its presence, of increasing the viscosity of the medium by at least 50 centipoise at 25°C and at a shear rate of 1 s "1 .
- the thickening agent has, at 1% in water or a 50/50 water/alcohol mixture by weight at 25°C, a viscosity of greater than 100 centipoise at a shear rate of 1 s "1 . These viscosities may be measured in particular with viscometers or rheometers with cone-plate geometry.
- the thickening and/or gelling agents suitable for the compositions of the invention are well known in the art and may be selected from crosslinked polyacrylic acids, poly(oxyalkylene)glycols, poly(oxyalkylene)glycol esters, alginates, bio saccharides, starches and derivatives thereof such as distarch phosphate and carboxymethylstarch, natural gums such as xanthane, guar, carouba gums, scleroglucans, chitin and chitosan derivatives, carraghenans, modified or unmodified celluloses such as hydroxypropyl guar gum, methylhydroxyethylcellulose, hydroxypropylmethyl cellulose and hydroxyethyl cellulose, clays, and mixtures thereof.
- gelling agents especially that are in the aqueous phase
- concentration of thickening agents and/or gelling agents may vary from 0.01 to 4%, and preferably from 0.1 to 2% by weight relative to the total weight of the composition.
- compositions used in the invention may also comprise cosmetically acceptable adjuvants, such as for example penetrants, fragrances, dyes, plasticizers, buffers, and various typical adjuvants such as ceramides, pseudoceramides, vitamins or provitamins such as panthenol, opacifiers, reducing agents, preservatives, mineral fillers, pearlescent agents, flakes, sunscreens, proteins, moisturizers, emollients, demulcents, anti- foaming agents, antiperspirants, free-radical scavengers, bactericides, sequestrants, anti- dandruff agents, antioxidants, basifying agents, acidifying agents and any other additive conventionally used in cosmetic compositions intended to be applied to hair.
- cosmetically acceptable adjuvants such as for example penetrants, fragrances, dyes, plasticizers, buffers, and various typical adjuvants such as ceramides, pseudoceramides, vitamins or provitamins such as panthenol, o
- a subject of the present invention is a hair styling device comprising:
- a support comprising a plurality of cavities that can hold packets by capillary action or otherwise, preferably droplets of a composition
- a hair care composition comprising at least one setting agent, held by capillary action or otherwise in the cavities of the support.
- the hair care composition is liquid or comprises a liquid phase.
- the support may be rigid, semi-rigid or flexible.
- the support comprises or is preferably made of a non-absorbent material.
- “Non-absorbent” is understood to mean intrinsically impermeable to the composition, i.e. not allowing diffusion of the composition inside it nor the destruction of packets or droplets of composition.
- the non-absorbent material may be a thermoplastic or metallic material, in particular selected from polyolefms, polyamides including nylons, polyester, natural fibers, stainless steel, ceramics.
- the support may be constituted by or comprise an applicator portion, for example a flexible applicator portion, of relatively low thickness.
- the applicator portion is preferably crossed through by the cavities, which are separated by partitions made of a preferably non-absorbent material, for example thermoplastic or metallic.
- the applicator portion comprises studs (also called pins) or other portions in relief that include the cavities.
- the cavities may be situated at the tip end of the portions in relief, for example one cavity forming a hollow tip at the end of a portion in relief.
- the length of the portions in relief may be comprised between.2 and.200mm.
- the hollow tip may have a round shape, whose concavity is directed outwards.
- the applicator portion can hold droplets of the composition to be applied. To allow the transfer of the droplets of composition onto the hair, the applicator portion may be directed to the hair, even put in contact with the hair, as mentioned previously.
- the applicator portion may be selected from the following list: a mesh, a grid in particular a molded grid, a perforated membrane, in particular a perforated nonwoven, a low-thickness foam obtained for example by slicing a cellular material, a woven, a perforated film, in particular plastic or metallized, a network of studs.
- the support may be translucent, being in particular constituted of a grid whose mesh can be seen through, specifically comprising mesh with width between 100 ⁇ and 5 mm.
- the applicator portion even the support, may be vinyl-based, PVA- or PVP- based, pseudolatex such as acrylic polymers, polyurethanes, latex elastomers, this list being non-limiting.
- the cavities may be larger with opening less than or equal to 5 mm, preferably between 10 ⁇ and 3 mm, even between 100 ⁇ and 2 mm.
- the cavities may all have the same dimensions for a given support.
- the dimensions of the cavities may be adapted to the rheology and surface tension of the composition.
- the number of cavities may vary from 1 to 100,000, preferably from 50 to 50,000, more preferably from 100 to 5000, the cavities extending for example on a surface area of the support varying from 1 to 1000 cm 2 , preferably from 5 to 500 cm 2 .
- the distribution and/or the size of the cavities is irregular, in particular when depositing the composition according to a specific arrangement is the aim.
- the cavities are for example made by perforating a membrane according to a specific arrangement.
- the applicator portion receives a treatment, in particular a selective printing by screen printing for example, to close, optionally partially, cavities around arrangements to be made.
- a treatment in particular a selective printing by screen printing for example, to close, optionally partially, cavities around arrangements to be made.
- the support may comprise a frame arranged at least partially around the applicator portion and preferably all the way around.
- the frame may be rigid, semi-rigid or flexible.
- the frame may comprise a synthetic material, in particular a thermoplastic elastomer or a foam with closed cells, in particular NBR or SBR or a natural or synthetic rubber.
- the frame is more rigid than the applicator portion and can hold it in a specific shape, for example measurably planar.
- the frame may be fixed to the applicator portion by any suitable means, in particular by gluing, heat-sealing, crimping.
- the applicator portion may be made by molding or overmolding with the frame, in the same material or in a different material.
- the device may comprise a flexible membrane, and more generally any intermediate part between the user and the applicator portion, extending behind the applicator portion.
- This membrane or intermediate portion is for example made of a soft, non-absorbent material, impermeable to the hair care composition in liquid form.
- the frame and/or the membrane or intermediate portion may define a gripping surface for the device, and in particular of the support.
- a frame and/or a membrane or intermediate portion impermeable to the composition may make it easier to handle the support, particularly when it is reloaded with composition and, when it is put on the hair, fingers are not in contact with the composition, which may stain.
- the support is reloaded with composition before each use.
- the device may comprise a container containing the composition.
- the container may be a case housing a sponge soaked with composition, that is accordingly available to load the applicator portion, which is for example in the form of a mesh or grid. The applicator portion then has to be pressed onto the sponge to load it with composition.
- the invention is not limited to a specific container to contain the composition that must load the support.
- the device may comprise several supports, differing by the size and/or distribution of cavities, in particular their surface density. The user may then select, for a specific use, in particular shaping, styling, hair design, setting or touch ups, the best suited support.
- the support may also be preloaded with composition.
- the support is supplied to the user preloaded with composition, for example in a sealed packaging.
- the support preloaded or not, is presented as a roll, with optional perforation to make it easier to separate the sheets of support.
- the sheets may be for single use.
- the support is presented as a pile or roll of sheets each defining an applicator portion prefilled with the composition to be applied.
- This method of distribution is particularly interesting in a professional setting; it is hygienic and means for example that a distribution of the composition on the hair can be reproduced easily according to a specific pattern defined as a function of the targeted hair style. In the presence of active cavities, these may be controlled according to a pattern that is to be made on the hair.
- the pile or roll of sheets may be submerged, if need be, in a container that contains the composition to be applied.
- the sheets are soaked with the composition without being submerged in it.
- a subject of the present invention is a hair styling or makeup system comprising:
- a support comprising a plurality of cavities that can hold packets by capillary action or otherwise, preferably droplets of a composition, in particular as defined hereinbefore,
- composition preferably comprising at least one setting agent
- the gas blowing on the support causing the ejection and/or transfer of packets, preferably droplets, of the support toward the area to be treated.
- the support may comprise a flexible or non flexible application part.
- the support may comprise an application part comprising studs or other portions in relief.
- the invention delivers a perfectly directional hair styling or makeup system, without losses or stains.
- the hair styling or makeup system comprises for example one or more stems that are attached at one end to the gas blowing system, for example an aerosol can, and at the other end to the support. These stems are for example molded of a single part with a support frame. The stem length is selected so that the gas jet emitted by the gas blowing system forces the droplets of composition to leave the cavities in the direction of the hair.
- the aerosol can may contain compressed air and be recharged.
- the subject of the present invention is also a process of hair styling or makeup using a device or a hair styling or makeup system as described previously.
- FIGS. 1A and IB illustrate a hair styling process according to the invention.
- FIG. 2A to 2F are different views of supports according to the invention
- figures 3B and 3F are cross sections along IIIB of figure 2B and along III
- figure 4 shows a cross section of a device according to the invention
- - figure 5 shows in perspective a hair styling system according to the invention
- figure 6 illustrates a hair styling process using the system shown in figure
- figure 7 shows a cross section of a variant of embodiment for the support according to the invention.
- the process according to the invention may be implemented directly by the consumer, to position or touch up his or her hair. In an alternative way, it can be used in a professional setting, as illustrated for example in figures 1A and IB.
- Figure 1A represents a support 2 according to the invention not comprising a frame, in the form of a mesh of non-absorbent material, for example of nylon, holding droplets G of a composition P containing a setting agent, that the hair stylist has placed on the hair.
- the hair stylist may facilitate the transfer of droplets onto the hair using an air jet, for example a cold air jet produced by an aerosol can filled with compressed air, not shown.
- Figure IB shows that the hair stylist, after having reloaded the support with the composition, may repeat the operation by placing the mesh on another part of the hair.
- the support 2 comprises a plurality of cavities 3 in which droplets G of the composition to be applied are held.
- the support 2 comprises an applicator portion 20 formed of a metal grid, held by a frame 9.
- the shape of the cavities and the nature of the support govern the size of the drops, how many there are, how they transfer and how they are spaced once deposited on the hair.
- Figure 2B shows a zoom of the detail of area I of figure 2A.
- droplets G are very numerous and may agglomerate on hair. This type of support is interesting in particular to obtain strong setting, which lasts a long time.
- each cavity 3 may be defined by a plurality of interconnected partitions 4, extending in multiple directions.
- Each cavity may be defined for example when observed face on by a succession of four partitions 4 or more, each measurably rectilinear, forming a loop.
- the partitions may be formed by the filaments of a grid as in the examples illustrated in figures 2A-2D.
- the cavities may present any shape, in particular a round, square, rectangular, hexagonal or polygonal shape.
- the largest opening dimension D is preferably less than or equal to 2 mm.
- Figure 3B illustrates in cross section IIIB the applicator portion 20 of the support 2 of figure 2B presented in the form of a grid, in which the cavities 3 are separated by partitions 4 formed by the threads of the grid.
- the diameter of the threads corresponds in the case of a grid to the width l p of the partitions 4 defining the cavities and to the thickness e m of the applicator portion 20.
- Thickness e m of the applicator portion 20 may lies for example between 10 ⁇ and 5 mm.
- the droplets G are held by capillary action in the cavities 3.
- the device 1 illustrated in figure 2F comprises an application portion 20 formed by a plurality of portions in relief (e.g. studs) with a hollow tip forming a cavity 3 to hold a droplet G of the composition before application.
- the portions in relief are elongate in shape, for example cylindrical, as illustrated in Figure 3G, or conical.
- opening size D of cavities 3 equals 1.5mm
- the applicator portion 20 consists of a network of studs molded on an intermediate part 25 serving as a gripping surface for the device 1.
- the applicator portion 20 of the illustrated device has a disk shape of about 10 cm in diameter, the intermediate part 25 being about 14 cm in diameter and 5mm in thickness e f .
- the height of the portions in relief is 5mm in the illustrated embodiment.
- Other embodiments may comprise longer studs forming application portion with a thickness e m lying for example between 2mm and 200 mm.
- cross sections of the portions in relief may present any shape, in particular a round, square, rectangular, hexagonal or other polygonal shape.
- Cavities 3, formed at the end of the portions in relief have for example a concavity of a radius between 0.2 and 4 mm, for example.
- the device may comprise more than 100 pins or studs.
- the pins or studs may all have a same height, as shown.
- the network may be regular (i.e. with same step p' between two studs), as shown, or irregular with varying step.
- Figure 4 shows a case 7 comprising a cover 8 and a container 70 formed of a sponge 5 containing the composition P to be applied.
- the support 2 is in the example illustrated formed of an applicator portion 20 in the form of a disk about 6 cm in diameter that treats a quarter of the hair after having been loaded once.
- the support 2 may be placed on the hair and tapped lightly, which deposits the drops of product on the hair.
- the gesture is very feminine since it recalls the powder puff used to powder one's face. This embodiment is suited to setting and "touching up” the hair all day long.
- a same device 1 may comprise several distinct supports 2, for example grids presenting different meshes as in the example illustrated.
- a first support 2 may be arranged in the base 75 of the case 7, above the sponge 5 when it is not used.
- the example illustrated further comprises two extra supports 2, stored when they are not used in a housing 85 of the cover 8 of the case 7.
- the housing 85 is closed by a closure lid capsule 80.
- the cover 8 may screw onto the base 75 of the case to close it. Any closure system known to a person skilled in the art, both for the cover 8 and for the capsule 80, may be used.
- the supports comprise an applicator portion and an intermediate portion that is impermeable to composition P defining a gripping surface that makes handling them easier.
- the cover 8 does not comprise a housing and the device 1 comprises a single support.
- Figure 5 illustrates a hair styling system 10 comprising a support 2 connected by an attachment system 15 to a gas source 30 constituted of a compressed air can.
- the attachment system 15 illustrated comprises three stems 16 connecting the frame 9 of the support 2 to the nozzle 35 of the source 30.
- the stems 16 hold the support 2 at a distance L from the nozzle 35.
- the person skilled in the art may select any other suitable attachment system without exiting the scope of the invention.
- the distance L between the gas outlet nozzle 35 and the support 2 is for example between 4 and 30 cm.
- Figure 6 illustrates a user using the hair styling system 10 according to figure
- the user shapes his or her hair using a comb while using the system 10, and accordingly easily sets his or her hair tress by tress. He or she reloads the applicator portion 20 from a container that is not shown.
- the support illustrated on figure 7 comprises an applicator portion 20 of thickness e m and an intermediate portion 25 of thickness e f defining a gripping surface, impermeable to the composition P, but permeable to air so that, if it is desired, an air jet may be used to make the transfer of droplets G from cavities 3 onto the hair easier.
- the gripping surface 25 extends further on the sides of the applicator portion 20, thus making handling easier.
- the invention is in particular not limited to hair styling or to hair treatment.
- a process of making up according to the invention may for example use an adhesive composition and allow making up with the transfer of sticky droplets then application of particles or other compounds that stick to the skin by virtue of the droplets.
- the process comprises the transfer of droplets of a colored composition that forms "pixels" or dots with a distribution that allows arrangements or gradients to be made on the body, in particular the face, the cheeks for example or to create pixelated effects for example on the lips.
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Abstract
La présente invention porte sur un procédé pour le traitement non thérapeutique de substances kératiniques humaines ou de membranes muqueuses humaines, lequel procédé comprend l'étape consistant à transférer sur des substances kératiniques humaines ou des membranes muqueuses humaines des paquets, de préférence des gouttelettes (G), d'une composition (P), maintenus par action capillaire ou autrement dans des cavités (3) dans un support (2), par mise en contact dudit support (2) avec des substances kératiniques ou des membranes muqueuses et/ou par éjection desdits paquets, de préférence desdites gouttelettes, à partir du support (2) par action mécanique.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/984,077 US20140161737A1 (en) | 2011-02-08 | 2012-02-08 | Process for applying a hair care composition to hair |
| ES12705443.5T ES2681676T3 (es) | 2011-02-08 | 2012-02-08 | Proceso para aplicar una composición de cuidado del cabello al cabello |
| EP12705443.5A EP2672859B1 (fr) | 2011-02-08 | 2012-02-08 | Procédé d'application d'une composition de soins capillaires sur les cheveux |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1151005A FR2971157B1 (fr) | 2011-02-08 | 2011-02-08 | Procede d'application d'une composition capillaire sur les cheveux. |
| FR1151005 | 2011-02-08 | ||
| US201161450826P | 2011-03-09 | 2011-03-09 | |
| US61/450,826 | 2011-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2012107887A2 true WO2012107887A2 (fr) | 2012-08-16 |
| WO2012107887A3 WO2012107887A3 (fr) | 2012-11-29 |
Family
ID=44548902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2012/050566 Ceased WO2012107887A2 (fr) | 2011-02-08 | 2012-02-08 | Procédé d'application d'une composition de soins capillaires sur les cheveux |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20140161737A1 (fr) |
| EP (1) | EP2672859B1 (fr) |
| ES (1) | ES2681676T3 (fr) |
| FR (1) | FR2971157B1 (fr) |
| WO (1) | WO2012107887A2 (fr) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3087637A1 (fr) | 2018-10-31 | 2020-05-01 | L'oreal | Procede d'application d'une composition de coiffage a agent fixant |
| FR3091473A1 (fr) | 2019-01-03 | 2020-07-10 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
| FR3091476A1 (fr) | 2019-01-03 | 2020-07-10 | L'oreal | Procédé d’application d’une composition de coiffage à agent fixant |
| FR3094613A1 (fr) | 2019-04-08 | 2020-10-09 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
| WO2020234469A1 (fr) | 2019-05-23 | 2020-11-26 | L'oreal | Applicateur pour appliquer un produit de soins capillaires, et procédé d'application associé |
| WO2020234304A1 (fr) | 2019-05-23 | 2020-11-26 | L'oreal | Applicateur pour appliquer un produit de soins capillaires, et procédé d'application associé |
| WO2020234297A1 (fr) | 2019-05-23 | 2020-11-26 | L'oreal | Applicateur pour appliquer un produit capillaire, et procédé d'application associé |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013026630A2 (fr) * | 2011-08-19 | 2013-02-28 | Unilever Plc | Kit de lavage |
| FR3041511B1 (fr) * | 2015-09-28 | 2017-12-01 | Capsum | Dispositif de conditionnement d'une emulsion |
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| FR1222944A (fr) | 1958-04-15 | 1960-06-14 | Hoechst Ag | Polymères greffés et leur procédé de préparation |
| GB839805A (en) | 1957-06-10 | 1960-06-29 | Monsanto Chemicals | Sprayable compositions |
| FR1400366A (fr) | 1963-05-15 | 1965-05-28 | Oreal | Nouveaux composés pouvant être utilisés en particulier pour le traitement des cheveux |
| FR1564110A (fr) | 1967-03-23 | 1969-04-18 | ||
| FR1580545A (fr) | 1967-07-28 | 1969-09-05 | ||
| US3589578A (en) | 1968-01-20 | 1971-06-29 | Monforts Fa A | Tension-relieving device for stretchable sheet material |
| FR2077143A5 (fr) | 1970-01-30 | 1971-10-15 | Gaf Corp | |
| DE2330956A1 (de) | 1972-06-20 | 1974-01-10 | Oreal | Kationische gepfropfte und vernetzte mischpolymerisate, verfahren zu ihrer herstellung und ihre verwendung in kosmetischen zubereitungen |
| FR2198719A1 (fr) | 1972-09-11 | 1974-04-05 | Hobbs R Ltd | |
| US3836537A (en) | 1970-10-07 | 1974-09-17 | Minnesota Mining & Mfg | Zwitterionic polymer hairsetting compositions and method of using same |
| FR2265781A1 (fr) | 1974-04-01 | 1975-10-24 | Oreal | |
| FR2265782A1 (fr) | 1974-04-01 | 1975-10-24 | Oreal | |
| US4031307A (en) | 1976-05-03 | 1977-06-21 | Celanese Corporation | Cationic polygalactomannan compositions |
| FR2350384A1 (fr) | 1976-05-06 | 1977-12-02 | Berger Jenson & Nicholson Ltd | Produits de revetement comprenant un latex aqueux d'un liant resineux |
| FR2357241A2 (fr) | 1976-07-08 | 1978-02-03 | Oreal | Nouvelle composition cosmetique a base de copolymeres anhydrides mono-esterifies ou mono-amidifies, copolymeres nouveaux et leur procede de preparation |
| US4128631A (en) | 1977-02-16 | 1978-12-05 | General Mills Chemicals, Inc. | Method of imparting lubricity to keratinous substrates and mucous membranes |
| US4131576A (en) | 1977-12-15 | 1978-12-26 | National Starch And Chemical Corporation | Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system |
| FR2393573A1 (fr) | 1977-06-10 | 1979-01-05 | Gaf Corp | Preparations capillaires contenant un copolymere de vinylpyrrolidone |
| FR2439798A1 (fr) | 1978-10-27 | 1980-05-23 | Oreal | Nouveaux copolymeres utilisables en cosmetique, notamment dans des laques et lotions de mises en plis |
| EP0080976A1 (fr) | 1981-11-30 | 1983-06-08 | Ciba-Geigy Ag | Mélanges des sels polymères acryliques d'ammonium quaternaire, de sels mono- ou oligomères d'ammonium quaternaire et de tensioactifs, leur préparation et leur utilisation dans des compositions cosmétiques |
| US4693935A (en) | 1986-05-19 | 1987-09-15 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith |
| US4728571A (en) | 1985-07-19 | 1988-03-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer release coating sheets and adhesive tapes |
| US4972037A (en) | 1989-08-07 | 1990-11-20 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith |
| JPH02295912A (ja) | 1989-05-10 | 1990-12-06 | Shiseido Co Ltd | 肌用化粧料 |
| EP0412704A2 (fr) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Compositions pour traiter et fixer la chevelure |
| EP0412707A1 (fr) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Compositions pour le conditionnement et la mise en forme des cheveux |
| WO1993023009A1 (fr) | 1992-05-12 | 1993-11-25 | Minnesota Mining And Manufacturing Company | Polymeres utilises dans des compositions cosmetiques et des produits de soins |
| EP0582152A2 (fr) | 1992-07-28 | 1994-02-09 | Mitsubishi Chemical Corporation | Composition cosmétique pour les cheveux |
| WO1994003510A1 (fr) | 1992-07-29 | 1994-02-17 | Basf Aktiengesellschaft | Utilisation de polyurethannes solubles dans l'eau ou dispersibles dans l'eau comme adjuvants dans des preparations cosmetiques et pharmaceutiques, et polyurethannes renfermant des polyolpolylactiques incorpores par polymerisation |
| EP0619111A1 (fr) | 1993-04-06 | 1994-10-12 | National Starch and Chemical Investment Holding Corporation | Utilisation des polyuréthanes avec des groupes carboxyliques fonctionelle comme agent fixateur des cheveux |
| WO1995000578A1 (fr) | 1993-06-24 | 1995-01-05 | The Procter & Gamble Company | Copolymeres de polyolefine modifies au siloxane |
| EP0637600A1 (fr) | 1993-08-04 | 1995-02-08 | L'oreal | Nouveaux polyester-polyuréthannes, leur procédé de préparation, pseudo-latex réalisés à partir desdits polyester-polyuréthannes et leur utilisation dans des compositions cosmétiques |
| EP0640105A1 (fr) | 1992-05-15 | 1995-03-01 | The Procter & Gamble Company | Agents adhesifs contenant un polymere a greffe polysiloxane et leur compositions cosmetiques |
| EP0648485A1 (fr) | 1993-10-15 | 1995-04-19 | L'oreal | Vernis à ongles aqueux, contenant des particules de polyester-polyuréthanne anionique à l'état dispersé |
| EP0751162A1 (fr) | 1995-06-27 | 1997-01-02 | L'oreal | Utilisation dans et pour la fabrication de compositions cosmétiques ou dermatologiques de polycondensats séquencés polyuréthanes et/ou polyurées à greffons siliconés |
| FR2743297A1 (fr) | 1996-01-05 | 1997-07-11 | Oreal | Composition cosmetiques a base de polycondensats ionisables multisequences polysiloxane/polyurethane et/ou polyuree en solution et utilisation |
| US5761824A (en) | 1997-01-31 | 1998-06-09 | Ibc Usa, Inc. | Hair moisturizing attachment for use with a hair dryer |
| GB2419089A (en) | 2004-10-13 | 2006-04-19 | Jeremy Gordon Salter | Method of hair treatment and component therefor |
| US20060247585A1 (en) | 2004-11-17 | 2006-11-02 | Kelly Albert R | Disposable pads for applying and distributing substances to target surfaces |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1295647A1 (fr) * | 2001-09-24 | 2003-03-26 | The Technology Partnership Public Limited Company | Buses dans des membranes perforées et méthode de fabrication |
| US7322945B2 (en) * | 2003-11-18 | 2008-01-29 | Joseph C. Dunmore, Sr. | Heated lather shaving cream and oil applicator |
| US20080087293A1 (en) * | 2006-10-12 | 2008-04-17 | The Procter & Gamble Company | Hair treatment application system |
| US8407913B2 (en) * | 2007-09-27 | 2013-04-02 | Wahl Clipper Corporation | Conditioner infuser for hair dryer attachment |
| FR2933319B1 (fr) * | 2008-07-02 | 2010-08-13 | Oreal | Atomiseur piezoelectrique comprenant une composition liquide parfumante ; procede de parfumage |
| JP4872013B2 (ja) * | 2009-07-29 | 2012-02-08 | 花王株式会社 | 頭皮洗浄具 |
| WO2011075659A2 (fr) * | 2009-12-18 | 2011-06-23 | The Procter & Gamble Company | Composition de colorant capillaire moussante |
-
2011
- 2011-02-08 FR FR1151005A patent/FR2971157B1/fr not_active Expired - Fee Related
-
2012
- 2012-02-08 WO PCT/IB2012/050566 patent/WO2012107887A2/fr not_active Ceased
- 2012-02-08 US US13/984,077 patent/US20140161737A1/en not_active Abandoned
- 2012-02-08 ES ES12705443.5T patent/ES2681676T3/es active Active
- 2012-02-08 EP EP12705443.5A patent/EP2672859B1/fr active Active
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| US3589578A (en) | 1968-01-20 | 1971-06-29 | Monforts Fa A | Tension-relieving device for stretchable sheet material |
| FR2077143A5 (fr) | 1970-01-30 | 1971-10-15 | Gaf Corp | |
| US3836537A (en) | 1970-10-07 | 1974-09-17 | Minnesota Mining & Mfg | Zwitterionic polymer hairsetting compositions and method of using same |
| DE2330956A1 (de) | 1972-06-20 | 1974-01-10 | Oreal | Kationische gepfropfte und vernetzte mischpolymerisate, verfahren zu ihrer herstellung und ihre verwendung in kosmetischen zubereitungen |
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| FR2265781A1 (fr) | 1974-04-01 | 1975-10-24 | Oreal | |
| FR2265782A1 (fr) | 1974-04-01 | 1975-10-24 | Oreal | |
| US4031307A (en) | 1976-05-03 | 1977-06-21 | Celanese Corporation | Cationic polygalactomannan compositions |
| FR2350384A1 (fr) | 1976-05-06 | 1977-12-02 | Berger Jenson & Nicholson Ltd | Produits de revetement comprenant un latex aqueux d'un liant resineux |
| FR2357241A2 (fr) | 1976-07-08 | 1978-02-03 | Oreal | Nouvelle composition cosmetique a base de copolymeres anhydrides mono-esterifies ou mono-amidifies, copolymeres nouveaux et leur procede de preparation |
| US4128631A (en) | 1977-02-16 | 1978-12-05 | General Mills Chemicals, Inc. | Method of imparting lubricity to keratinous substrates and mucous membranes |
| FR2393573A1 (fr) | 1977-06-10 | 1979-01-05 | Gaf Corp | Preparations capillaires contenant un copolymere de vinylpyrrolidone |
| US4131576A (en) | 1977-12-15 | 1978-12-26 | National Starch And Chemical Corporation | Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system |
| FR2439798A1 (fr) | 1978-10-27 | 1980-05-23 | Oreal | Nouveaux copolymeres utilisables en cosmetique, notamment dans des laques et lotions de mises en plis |
| EP0080976A1 (fr) | 1981-11-30 | 1983-06-08 | Ciba-Geigy Ag | Mélanges des sels polymères acryliques d'ammonium quaternaire, de sels mono- ou oligomères d'ammonium quaternaire et de tensioactifs, leur préparation et leur utilisation dans des compositions cosmétiques |
| US4728571A (en) | 1985-07-19 | 1988-03-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer release coating sheets and adhesive tapes |
| US4693935A (en) | 1986-05-19 | 1987-09-15 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith |
| JPH02295912A (ja) | 1989-05-10 | 1990-12-06 | Shiseido Co Ltd | 肌用化粧料 |
| US4972037A (en) | 1989-08-07 | 1990-11-20 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith |
| EP0412704A2 (fr) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Compositions pour traiter et fixer la chevelure |
| EP0412707A1 (fr) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Compositions pour le conditionnement et la mise en forme des cheveux |
| WO1993023009A1 (fr) | 1992-05-12 | 1993-11-25 | Minnesota Mining And Manufacturing Company | Polymeres utilises dans des compositions cosmetiques et des produits de soins |
| EP0640105A1 (fr) | 1992-05-15 | 1995-03-01 | The Procter & Gamble Company | Agents adhesifs contenant un polymere a greffe polysiloxane et leur compositions cosmetiques |
| EP0582152A2 (fr) | 1992-07-28 | 1994-02-09 | Mitsubishi Chemical Corporation | Composition cosmétique pour les cheveux |
| WO1994003510A1 (fr) | 1992-07-29 | 1994-02-17 | Basf Aktiengesellschaft | Utilisation de polyurethannes solubles dans l'eau ou dispersibles dans l'eau comme adjuvants dans des preparations cosmetiques et pharmaceutiques, et polyurethannes renfermant des polyolpolylactiques incorpores par polymerisation |
| EP0656021A1 (fr) | 1992-07-29 | 1995-06-07 | Basf Ag | Utilisation de polyurethannes solubles dans l'eau ou dispersibles dans l'eau comme adjuvants dans des preparations cosmetiques et pharmaceutiques, et polyurethannes renfermant des polyolpolylactiques incorpores par polymerisation. |
| EP0619111A1 (fr) | 1993-04-06 | 1994-10-12 | National Starch and Chemical Investment Holding Corporation | Utilisation des polyuréthanes avec des groupes carboxyliques fonctionelle comme agent fixateur des cheveux |
| WO1995000578A1 (fr) | 1993-06-24 | 1995-01-05 | The Procter & Gamble Company | Copolymeres de polyolefine modifies au siloxane |
| EP0637600A1 (fr) | 1993-08-04 | 1995-02-08 | L'oreal | Nouveaux polyester-polyuréthannes, leur procédé de préparation, pseudo-latex réalisés à partir desdits polyester-polyuréthannes et leur utilisation dans des compositions cosmétiques |
| EP0648485A1 (fr) | 1993-10-15 | 1995-04-19 | L'oreal | Vernis à ongles aqueux, contenant des particules de polyester-polyuréthanne anionique à l'état dispersé |
| EP0751162A1 (fr) | 1995-06-27 | 1997-01-02 | L'oreal | Utilisation dans et pour la fabrication de compositions cosmétiques ou dermatologiques de polycondensats séquencés polyuréthanes et/ou polyurées à greffons siliconés |
| FR2743297A1 (fr) | 1996-01-05 | 1997-07-11 | Oreal | Composition cosmetiques a base de polycondensats ionisables multisequences polysiloxane/polyurethane et/ou polyuree en solution et utilisation |
| US5761824A (en) | 1997-01-31 | 1998-06-09 | Ibc Usa, Inc. | Hair moisturizing attachment for use with a hair dryer |
| GB2419089A (en) | 2004-10-13 | 2006-04-19 | Jeremy Gordon Salter | Method of hair treatment and component therefor |
| US20060247585A1 (en) | 2004-11-17 | 2006-11-02 | Kelly Albert R | Disposable pads for applying and distributing substances to target surfaces |
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|---|---|---|---|---|
| FR3087637A1 (fr) | 2018-10-31 | 2020-05-01 | L'oreal | Procede d'application d'une composition de coiffage a agent fixant |
| WO2020089387A1 (fr) | 2018-10-31 | 2020-05-07 | L'oreal | Procédé d'application d'une composition de coiffage comprenant un agent fixant |
| FR3091473A1 (fr) | 2019-01-03 | 2020-07-10 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
| FR3091476A1 (fr) | 2019-01-03 | 2020-07-10 | L'oreal | Procédé d’application d’une composition de coiffage à agent fixant |
| FR3094613A1 (fr) | 2019-04-08 | 2020-10-09 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
| WO2020208034A1 (fr) | 2019-04-08 | 2020-10-15 | L'oreal | Applicateur pour appliquer un produit capillaire, et procédé d'application associé |
| WO2020234469A1 (fr) | 2019-05-23 | 2020-11-26 | L'oreal | Applicateur pour appliquer un produit de soins capillaires, et procédé d'application associé |
| WO2020234304A1 (fr) | 2019-05-23 | 2020-11-26 | L'oreal | Applicateur pour appliquer un produit de soins capillaires, et procédé d'application associé |
| WO2020234297A1 (fr) | 2019-05-23 | 2020-11-26 | L'oreal | Applicateur pour appliquer un produit capillaire, et procédé d'application associé |
| FR3096241A1 (fr) | 2019-05-23 | 2020-11-27 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
| FR3096240A1 (fr) | 2019-05-23 | 2020-11-27 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
| FR3096239A1 (fr) | 2019-05-23 | 2020-11-27 | L'oreal | Applicateur pour l’application de produit capillaire, et procédé d’application associé |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140161737A1 (en) | 2014-06-12 |
| EP2672859B1 (fr) | 2018-05-16 |
| ES2681676T3 (es) | 2018-09-14 |
| WO2012107887A3 (fr) | 2012-11-29 |
| EP2672859A2 (fr) | 2013-12-18 |
| FR2971157A1 (fr) | 2012-08-10 |
| FR2971157B1 (fr) | 2013-10-04 |
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